Method of fabricating a trapping-mode

ABSTRACT

Photodetectors that produce detectivities close to the theoretical maximum detectivity include an electrically insulating substrate carrying a body of semiconductor material that includes a region of first conductivity type and a region of second conductivity type where the region of first conductivity type overlies and covers the junction with the region of second conductivity type and where the junction between the first and second regions separates minority carriers in the region of second conductivity type from majority carriers in the region of first conductivity type. These photodetectors produce high detectivities where radiation incident on the detectors has wavelengths in the range of about 1 to about 25 microns or more, particularly under low background conditions.

This is a division of application Ser. No. 545,108 filed Jun 27, 1990, U.S. Pat. No. 5,079,610, which was a continuation of application Ser. No. 804,719, filed Dec. 5, 1985, now abandoned.

FIELD OF THE INVENTION

This invention relates to photodetectors for producing detectable signals from incident radiation such as infrared radiation having wavelengths in the range of about 1 to about 25 microns, or more, particularly where the radiation appears in low background level energy fields, such as, for example, fields with background flux levels less than about 10¹⁷ photons/cm² -sec.

BACKGROUND OF THE INVENTION

Photodetectors made of mercury cadmium telluride semiconductor material are disclosed in U. S. Pat. No. 3,949,223, issued Apr. 6, 1976, and entitled, "Monolithic Photoconductive Detector Array."

As the '223 patent discloses, when radiation of the proper energy falls upon a semiconductor, its conductivity increases. Energy supplied to the semiconductor causes covalent bonds to break, and electron/hole pairs (also called majority/minority carriers) in excess of those generated thermally are created. These increased current carriers increase the conductivity of the material. This so-called "photoconductive effect" in semiconductor materials is utilized in photodetectors.

A photodetector can be, for example, a bar of semiconductor material having electrical contacts at its ends. In one form, the photodetector is connected in series with a direct current voltage source and a load resistor. The change in conductivity of the detector in response to incident radiation is sensed in one of two ways. If the resistance of the load resistor exceeds the resistance of the detector, the device operates in the "constant current mode," since the current to the detector is essentially constant. In this mode, the change in conductivity of the detector is usually sensed by measuring the voltage across the detector.

If the resistance of the load resistor is less than the resistance of the detector, the detector is operating in the "constant voltage mode," since the voltage across the detector is essentially constant. The change in the conductivity of the detector is usually sensed by measuring the voltage across the resistor.

Of these two modes, the constant current mode finds wider use in detectors made from semiconductor materials having low resistivity.

Photodetectors, and particularly arrays of such detectors, have many applications. One application is in the detection of infrared radiation. Infrared sensitive photodetector arrays are used for various heat and object sensing applications.

One widely used infrared-sensitive photodetective material is mercury cadmium telluride, which consists of a mixture of cadmium telluride and mercury telluride. Cadmium telluride is a wide-gap semiconductor (E_(g) =1.6 eV), and mercury telluride is a semi-metal having a "negative energy gap" of about minus 0.3 eV. The energy gap of the alloy varies monotonically with x, the mole fraction of cadmium telluride in the alloy, Hg_(1-x) Cd_(x) Te. By properly selecting x, it is possible to obtain mercury cadmium telluride detectors having a peak response at any of a wide range of infrared wavelengths.

Mercury cadmium telluride photodetector arrays are now made by mounting a mercury cadmium telluride crystal on substrates with an epoxy. The thickness of the mercury cadmium telluride is then reduced to about 10 microns by lapping, polishing and etching. The detectors are then delineated and isolated by masking, and then cutting or etching. Electrical leads are attached to opposite ends of each of the individual detector elements, or to one end of each and a common.

Other methods for making such photodetectors are disclosed in the '223 patent. None of these methods is known to produce a detector that operates close to the theoretical maximum detectivity for radiation wavelengths in the range of about 1 to about 25 microns or more, particularly for wavelengths in the range of about 10 to about 25 microns or more, and particularly where such radiation appears in low background levels such as those having less than about 10¹⁷ photons/cm² -sec.

SUMMARY OF THE INVENTION

The photodetectors of this invention produce detectivities close to the theoretical maximum detectivity of 2.52×10¹⁸ λη/Q_(B))^(1/2) cmHz^(1/2) /Watt, where η is the quantum efficiency, and Q_(B) is the background photon flux, and λ is the wavelength of the radiation incident on the detector, and at least about 2×10¹⁷ λη/Q_(B))^(1/2) cmHz^(1/2) /Watt, where the radiation incident on the detectors is in the range of about 1 microns to about 25 microns or more, more particularly in the range of about 10 microns to about 25 microns or more. These detectors are particularly effective in producing signals from such incident radiation under low background radiation conditions, meaning radiation flux levels of less than about 10¹⁷ photons/cm² -sec, and where the temperature under which the detector operates is sufficiently low to minimize thermal generation and recombination of excess carriers. In preferred embodiments, the duration of the signals produced by the new photodetectors at background levels in the range of about 10.sup. 10 to about 10¹³ photons/cm² -sec is at least about 50 microseconds and ranges as high as 100 microseconds or higher.

The new photodetectors comprise a substrate that is electrically insulating, such as a dielectric or wide band-gap semiconductor, attached to a body of semiconductor material comprising a region of first conductivity type and a region of a second, opposite conductivity type where the first region overlies the second. The region of first conductivity type has a narrow energy band-gap. The region of second, opposite conductivity type may have an energy band-gap substantially the same as, or different from the region of first conductivity type. This region of second type may have an energy band-gap that is substantially uniform and the same as or larger than the energy band-gap in the first region, or may vary, linearly or non-linearly, within the second region.

The method for making these new photodetectors comprises growing (depositing) a body of photoconductive material, epitaxially, on a substrate, and then annealing the epitaxially-grown photoconductive material to form the regions of first and second conductivity types atop the substrate. Where, as preferred, the photodetectors are made of mercury cadmium telluride material, the annealing takes place in a mercury vapor for a time sufficient to fill mercury vacancies in the portion of the semiconductor material referred to as the region of first conductivity type. After the annealing, the body of semiconductor material can be separated into a plurality of detectors by etching or other suitable technique.

After epitaxially growing the body of semiconductor material, an additional layer can be grown, epitaxially, atop the body of semiconductor material, to function as a means for minimizing diffusion of minority carriers to electrical contacts affixed to the top of the detectors.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a preferred embodiment of the method for making the new photodetectors of this invention;

FIGS. 2 and 3 illustrate the structure and behavior of two preferred embodiments of the new photodetectors of this invention; and

FIG. 4 shows a cross-sectional view of a detector array of the present invention.

BRIEF DESCRIPTION OF THE INVENTION

The methods for making photodetectors of the kind shown in the drawings preferably utilize a tellurium-rich or mercury-rich melt including mercury telluride and cadmium telluride in molten form. Photodetectors made from such melts comprise mercury cadmium telluride having the general formula Hg_(1-x) Cd_(x) Te, where x is in the range of about 0.95 to about 0.13. While this detailed description speaks in terms of mercury cadmium telluride photoconductors, the methods of the invention and/or the structures produced are applicable to the manufacture of photodetectors from other substances, such as III-V, II-VI and IV-VI semiconductor alloys, particularly those having narrow band-gap detecting layers.

FIG. 1 shows a preferred method for making the photodetectors of this invention from mercury cadmium telluride. A dielectric or wide band-gap semiconductor substrate (such as a cadmium telluride substrate) of relatively high resistivity, meaning a resistivity in the range of about 10³ to about 10⁸ ohm-cm, is covered with a tellurium melt solution including a predetermined amount of mercury and cadmium. This tellurium melt solution is permitted to cool on the substrate to a temperature where the melt is supersaturated, thereby forming an epitaxial layer of mercury cadmium telluride thereon. Preferably, the epitaxially-deposited layer of mercury cadmium telluride has an excess of tellurium atoms or a deficiency of mercury atoms (mercury vacancies) in the crystal layer such that its electrical type is dominated by hole carriers (p-type). The p-type concentration, as grown, is typically in the 10¹⁵ -10¹⁸ /cm³ range. Alternately, a mercury melt solution may be used to grow the layer having the same properties.

After formation of the epitaxial layer, the substrate carrying the semiconductive, epitaxially grown layer is annealed, preferably in a vapor comprising mercury, at a temperature in the range of about 200° C. to about 300° C., for a time in the range of about 0.1 to about 100 hours, or at least for a time sufficient to form an n-type detector layer at the surface of the epitaxial semiconductor body, while retaining a p-type layer beneath the n-type detector layer, and with the PN junction of the two layers extending substantially along the length of the p-type layer (i.e., the p-type trapping region underlies the entire n-type detection layer). By controlling the time and temperature of annealing, the detector can be made with greatest sensitivity to incident radiation. Time and temperature of the annealing can be adjusted, depending upon the ratio of mercury to cadmium, the thickness of the epitaxial layer, the temperature of growth, and other factors, to achieve maximum practicable sensitivity.

The n-type detector layer is lightly doped, meaning that the concentration of electrons is 5×10¹⁴ /cm³ or less so that the depletion layer width at the PN junction is substantial, and tunneling leakage, minimal. Also, the p-type region may lie substantially within a compositionally graded interface between the surface of the epitaxial layer and the substrate.

Before or after the annealing step, an additional layer may be deposited, epitaxially, on the surface of the n-type detector layer. This additional surface layer has a wider band-gap than the first epitaxial layer and can also be made of mercury cadmium telluride, preferably from a mercury melt solution including cadmium and tellurium, or may be made of cadmium telluride or other materials so that the layer prevents or minimizes diffusion of minority carriers to electrodes attached to the top of the detectors of this invention.

After the annealing step, or alternatively, after the annealing step and after application of the additional layer, the body of semiconductor material can be divided into a plurality of arrays by etching, or other known techniques. Thereafter, electrodes can be attached to each of the discrete detectors, or to as many as desired, to form a system including a plurality of the kind of detector shown in FIG. 4. Insulating layers may be added to this structure to control the surface electrical and optical properties.

As FIG. 4 shows, an electrical bias may be applied to a detector by connecting the two electrodes on the detector in series with a battery and load resistor. The electrical bias may be applied by other means, a few examples of which are a pulsing direct current source, an alternating current source, direct connection to a transistor, a microwave generator or from an integrated circuit multiplexer readout chip.

FIGS. 2 and 3 illustrate the electrical characteristics of the n-type and p-type layers in the photoconductors in their preferred mercury cadmium telluride embodiments. As they show, the n-type detector region atop the detectors has a small, relatively uniform energy band-gap which can be on the order of about 0.1 electron the n-type region. This low concentration produces a wide depletion layer at the PN junction which minimizes parasitic tunneling leakage currents between the p-type and n-type regions. For trapping minority carrier holes, the binding energy of the p-type region is substantially equal to the full energy band-gap of the detector layer, and may effectively be higher by virtue of being located within the compositionally graded interface between the surface of the epitaxial layer and the substrate. Accordingly, detectors made with this structure and by this method are less susceptible to performance degradation caused by tunneling leakage across the PN junction because of their wider depletion layers; less susceptible to surface leakage since the p-type layer may be more highly doped and located within a wider band-gap portion of the epitaxial layer; and more temperature stable because of the wider band-gap in the trapping p-type layer. One or more of these features, embodied in the new detectors, makes them superior to known detectors such as those disclosed in the '223 patent. 

What is claimed is:
 1. A method for making a photoconductive photodetector comprising epitaxially growing a body of semiconductor material on an electrically insulating substrate; annealing the resulting body of semiconductor material attached to said substrate for a time sufficient to form a region of first conductivity type substantially completely overlying a region of second conductivity type within said body of semiconductor material, and said photodetector having a detectivity of at least about 2×10¹⁷ λη/Q_(B))^(1/2) cmHz^(1/2) /Watt where the radiation incident on said photodetector is in the range of about 1 to about 25 microns or more, and where λ is the wavelength of radiation incident on said photodetector, Q_(B) is the background photon flux, and η is the quantum efficiency.
 2. The method of claim 1 further comprising etching said body of semiconductor material into a plurality of discrete detectors, and attaching, to at least one of said detectors, electrode means for deriving a photosignal from said photodetector.
 3. The method of claim 1 or claim 2 wherein the exitaxial growing is effected with a tellurium melt solution including an amount of mercury and cadmium.
 4. The method of claim 3 wherein said tellurium melt solution is permitted to cool on said substrate to a temperature at which the melt is supersaturated to form an epitaxial layer of mercury cadmium telluride on said substrate.
 5. The method of claim 1 or claim 2 wherein said expitaxial growing is carried out with a mercury melt solution including an amount of telleride and cadmium.
 6. The method of claim 5 wherein the mercury melt solution is permitted t cool on said substrate to a temperature at which the melt is supersaturated to form an epitaxial layer of mercury cadmium telluride thereon.
 7. The method of claim 1 wherein said annealing is carried out at a temperature in the range of about 200° C. to about 300° C. for a time in the range of about 0.1 to a bout 100 hours.
 8. The method of claim 1 wherein said annealing is carried out at least for a time sufficient to form an n-type detector layer at the surface of said body, and to form a p-type detector layer beneath said n-type detector layer, with the PN junction of the n-type and p-type layers extending substantially along the length of the p-type layer.
 9. A method for making a photoconductive photodetector having a detectivity of at least about 2×10¹⁷ λ(η/Q_(B))^(1/2) cmHz^(1/2) /Watt, where λ is the wavelength of radiation incident on said photodetector, Q_(B) is the background photon flux, and η is the quantum efficiency, and where the radiation incident on said photodetector is in the range of about 1 to a bout 25 microns, and comprising an electrically insulating substrate attached to a body of semiconductor material comprising a region of first conductivity type and a region of second, opposite conductivity type, said region of first conductivity type substantially completely overlying said region of second conductivity type, said region of second conductivity type tending to trap, and to separate minority carriers from majority carriers in said region of first conductivity type, said method comprising the steps of: epitaxially growing said body on said substrate; and annealing said body attached to said substrate for a time sufficient to form said regions of first and second conductivity types.
 10. The method of claim 9 further comprising subdividing said body into a plurality of said photodetectors.
 11. The method of claim 9 further comprising, before or after said annealing, epitaxially growing a layer of material over said body, said layer functioning to prevent minority carriers from drifting or diffusing to electrical contacts atop said layer.
 12. The method of claim 10 further comprising, before or after said annealing, epitaxially growing a layer of material over said body, said layer functioning to prevent minority carriers from drifting or diffusing to electrical contacts atop said layer.
 13. The method of claim 9 or claim 10 wherein the epitaxial growing is effected with a tellurium melt solution including an amount of mercury and cadmium.
 14. The method of claim 13 wherein said tellurium melt solution is permitted to cool on said substrate to a temperature at which the melt is supersaturated to form an epitaxial layer of mercury cadmium telluride on said substrate.
 15. The method of claim 9 or claim 10 wherein said epitaxial growing is carried out with a mercury melt solution including an amount of telleride and cadmium.
 16. The method of claim 15 wherein the mercury melt solution is permitted to cool on said substrate to a temperature at which the melt is supersaturated to form an epitaxial layer of mercury cadmium telluride on said substrate.
 17. The method of claim 9 or claim 10 wherein said annealing is carried out at a temperature in the range of about 200° C. to about 300° C. for a time in the range of about 0.1 to about 100 hours.
 18. The method of claim 9 or claim 10 wherein said annealing is carried out at least for a time sufficient to form an n-type detector layer at the surface of body, and to form a p-type detector layer beneath the n-type detector layer with the PN junction of the n-type and p-type layers extending substantially along the length of the p-type layer and along its side walls to said substrate.
 19. The method of claim 1 or claim 9 or claim 10 further comprising attaching electrodes to at least one of said photodetectors.
 20. The method of claim 1 or claim 9 or claim 10 comprising utilizing, as said semiconductor material during said epitaxial growing step, and alloy comprising metals selected from groups III and V, or metals selected from groups II and VI or metals selected from groups IV and VI of the periodic table of elements. 